Emergent room temperature polar phase in CaTiO                         3                          nanoparticles and single crystals

Mariola O. Ramirez; Tom T.A. Lummen; Irene Carrasco; Eftihia Barnes; Ulrich Aschauer; Dagmara Stefanska; Arnab Sen Gupta; Carmen De Las Heras; Hirofumi Akamatsu; Martin Holt; Pablo Molina; Andrew Barnes; Ryan C. Haislmaier; Przemyslaw J. Deren; Carlos Prieto; Luisa E. Bausá; Nicola A. Spaldin; Venkatraman Gopalan

doi:10.1063/1.5078706

Emergent room temperature polar phase in CaTiO ₃ nanoparticles and single crystals

Mariola O. Ramirez, Tom T.A. Lummen, Irene Carrasco, Eftihia Barnes, Ulrich Aschauer, Dagmara Stefanska, Arnab Sen Gupta, Carmen De Las Heras, Hirofumi Akamatsu, Martin Holt, Pablo Molina, Andrew Barnes, Ryan C. Haislmaier, Przemyslaw J. Deren, Carlos Prieto, Luisa E. Bausá, Nicola A. Spaldin, Venkatraman Gopalan

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Abstract

Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO ₃ , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T _C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO ₃ single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

Original language	English (US)
Article number	011103
Journal	APL Materials
Volume	7
Issue number	1
DOIs	https://doi.org/10.1063/1.5078706
State	Published - Jan 1 2019

All Science Journal Classification (ASJC) codes

General Materials Science
General Engineering

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10.1063/1.5078706

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Ramirez, M. O., Lummen, T. T. A., Carrasco, I., Barnes, E., Aschauer, U., Stefanska, D., Sen Gupta, A., De Las Heras, C., Akamatsu, H., Holt, M., Molina, P., Barnes, A., Haislmaier, R. C., Deren, P. J., Prieto, C., Bausá, L. E., Spaldin, N. A., & Gopalan, V. (2019). Emergent room temperature polar phase in CaTiO ₃ nanoparticles and single crystals APL Materials, 7(1), Article 011103. https://doi.org/10.1063/1.5078706

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title = " Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals ",

abstract = " Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.",

author = "Ramirez, {Mariola O.} and Lummen, {Tom T.A.} and Irene Carrasco and Eftihia Barnes and Ulrich Aschauer and Dagmara Stefanska and {Sen Gupta}, Arnab and {De Las Heras}, Carmen and Hirofumi Akamatsu and Martin Holt and Pablo Molina and Andrew Barnes and Haislmaier, {Ryan C.} and Deren, {Przemyslaw J.} and Carlos Prieto and Baus{\'a}, {Luisa E.} and Spaldin, {Nicola A.} and Venkatraman Gopalan",

note = "Publisher Copyright: {\textcopyright} 2019 Author(s).",

year = "2019",

month = jan,

day = "1",

doi = "10.1063/1.5078706",

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Ramirez, MO, Lummen, TTA, Carrasco, I, Barnes, E, Aschauer, U, Stefanska, D, Sen Gupta, A, De Las Heras, C, Akamatsu, H, Holt, M, Molina, P, Barnes, A, Haislmaier, RC, Deren, PJ, Prieto, C, Bausá, LE, Spaldin, NA & Gopalan, V 2019, ' Emergent room temperature polar phase in CaTiO ₃ nanoparticles and single crystals ', APL Materials, vol. 7, no. 1, 011103. https://doi.org/10.1063/1.5078706

TY - JOUR

T1 - Emergent room temperature polar phase in CaTiO 3 nanoparticles and single crystals

AU - Ramirez, Mariola O.

AU - Lummen, Tom T.A.

AU - Carrasco, Irene

AU - Barnes, Eftihia

AU - Aschauer, Ulrich

AU - Stefanska, Dagmara

AU - Sen Gupta, Arnab

AU - De Las Heras, Carmen

AU - Akamatsu, Hirofumi

AU - Holt, Martin

AU - Molina, Pablo

AU - Barnes, Andrew

AU - Haislmaier, Ryan C.

AU - Deren, Przemyslaw J.

AU - Prieto, Carlos

AU - Bausá, Luisa E.

AU - Spaldin, Nicola A.

AU - Gopalan, Venkatraman

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

AB - Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO 3 , the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T C = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO 3 single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

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JO - APL Materials

JF - APL Materials

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M1 - 011103

ER -

Emergent room temperature polar phase in CaTiO ₃ nanoparticles and single crystals

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